Straight-oil finishing composition and fiber yarn treated therewith

ABSTRACT

The invention relates to a straight-oil finishing composition comprising (A) 100 parts by weight of a polydimethylsiloxane oil or liquid paraffin having a viscosity of 3 to 70 mm 2 /s at 25 centigrade temperature; and (B) 0.5 to 100 parts by weight of an organopolysiloxane resin, which contains silanol groups and silicon-bonded alkoxy groups and wherein 20 mole % or more of all siloxane units are siloxane units represented by formula C 3 H 7 SiO 3/2 . This composition is useful for treating fiber yarn.

The invention relates to a straight-oil finishing composition useful fortreating fiber yarn which has improved storage stability and antistaticproperties, and a fiber yarn treated with the straight-oil finishingcomposition.

Various silicones find wide application in compositions of straight-oiltype treatment agents which receive their name because they are free ofany water or solvents. For example, it was proposed to use a mixture ofpolyamylsiloxane and polydimethylsiloxane as a lubricity-improving agentfor Spandex or similar elastic filaments (see Japanese PatentPublication (hereinafter referred to as Kokoku) No. Sho 42-8438).However, this oil-type treatment agent utilizes expensivepolyamylsiloxane. Furthermore, production of polyamylsiloxane may beaccompanied by variations in the amount of silanol groups contained inthis composition, as well as by variations in antistatic properties. Ayarn-treating composition obtained by combining a dimethylsiloxane oilwith the product of copolymerization of an MQ-type silicone resin and aDT-type silicone resin (see Kokoku No. Sho 63-12197) is also known. Adrawback of the aforementioned product of copolymerization of thesilicone resins is that copolymerization of the silicone resin isdifficult to control and that viscosity and antistatic properties of theobtained oil-type treatment agent are subject to variations.

One object of the invention to provide a straight-oil finishingcomposition, which has excellent storage stability and antistaticproperties.

The present invention relates to a straight-oil finishing compositioncomprising

(A) 100 parts by weight of a polydimethylsiloxane oil or liquid paraffinhaving a viscosity of 3 to 70 mm²/s at 25° C.; and

(B) 0.5 to 100 parts by weight of an organopolysiloxane resin whichcontains silanol groups and silicon-bonded alkoxy groups and 20 mole %or more of all siloxane units are represented by the formulaC₃H₇SiO_(3/2).

Among other things, this straight-oil finishing composition is usefulfor treating fiber yarn.

Component (A) is a main component of the composition of the invention.Its function is to impart smoothness to the fiber yarn. It isrecommended that the viscosity at 25° C. of the polydimethylsiloxane oilor liquid paraffin used in this component be within the range of 3 to 70mm²/s, preferably 3 to 50 mm²/s, and even more preferably, 3 to 30mm²/s. This is because, if the viscosity is below 3 mm²/s, the treatedfilament will have insufficient smoothness and if the viscosity exceeds70 mm²/s, too much of the treatment agent will adhere to the fiberfilament. The molecular structure of the polydimethylsiloxane oil ofcomponent (A) may be linear, cyclic, or partially branched. In the caseof a linear or partially branched molecular structure, it is recommendedto cap the molecular terminals with groups such as trialkylsiloxy orhydroxyl groups. The liquid paraffin useful in component (A) should havea high degree of purity, be colorless, and free of taste and odor.

Component (B) is a distinguishing component of the composition of theinvention and comprises an organopolysiloxane resin which is compatiblewith component (A). It is required that 20 mole % or more of allsiloxane units of this organopolysiloxane resin are represented by theformula C₃H₇SiO_(3/2) and that each molecule of the aforementioned resincontain one or more silanol groups and one or more silicon-bonded alkoxygroups. It is recommended that, in addition to the aforementionedsiloxane units, this component contain siloxane units of formula C₃H₇(HO)_(a)(R′O)_(b)SiO_((3-a-b)/2), where each R′ is an independentlyselected from alkyl group having 1 to 8 carbon atoms andalkyloxyalkylene group having 1 to 8 carbon atoms. Examples of alkylgroups useful as R′ include methyl, ethyl, propyl, butyl, hexyl, andoctyl. Examples of alkyloxyalkylene groups useful as R′ includemethoxyethylene, and ethoxyethylene. Most preferably from the point ofview of better compatibility with component (A), the R′ groups areindependently selected from all groups having 3 to 8 carbon atoms andalkyloxyalkylene groups having 3 to 8 carbon atoms, with alkyl groupshaving 3 to 8 carbon atoms being even more preferable. In the aboveformula, 0<a≦2; 0<b≦2 and 0<(a+b)≦2. It is recommended that the amountof silanol groups contained in component (B) be greater than the amountof alkoxy groups so a>b. Siloxane units of formula C₃H₇SiO_(3/2)preferably comprise 20 to 95 mole % of all siloxane units, whilesiloxane units of formula C₃H₇(HO)_(a)(R′O)_(b)SiO_((3-a-b)/2)preferably comprise 5 to 80 mole % of all siloxane units. The sum ofboth siloxane units should be 40 mole % or more of all siloxane unitsand preferably should occupy 60 to 100 mole %.

The organopolysiloxane resin can be represented by the following averageconstitutional formula:(C₃H₇SiO_(3/2))_(x)[C₃H₇(HO)_(a)(R′O)_(b)SiO_((3-a-b)/2)]_(y){R_(c)SiO_((4-c/2))}_(z),where R′, a and b are as defined above; each R is an independentlyselected phenyl group, alkyl group having 1 to 10 carbon atoms, hydroxylgroup, or alkoxy group. Examples of the alkyl group include methyl,ethyl, butyl, hexyl, octyl, and decyl. The most preferable from thepoint of view of compatibility with component (A) is methyl. Alkoxygroups may be the same as the aforementioned (R′O) groups; c is between0 and 3; x>0, y>0, z≧0, (x+y+z)=1 and x/(x+y+z)≧0.2. In addition, it isrecommended (x+y)/(x+y+z)≧0.4 and more preferably (x+y)/(x+y+z)≧0.6 Theweight-average molecular weight of component (B) should be within therange of 800 to 20000, preferably 1000 to 8000. Examples of component(B) include the following organopolysiloxane resins where a is 1 or 2and b is 1 or 2:(C₃H₇SiO_(3/2))_(0.5)[C₃H₇(HO)_(a)SiO_((3-a)/2)]_(0.3)[C₃H₇(C₂H₅O)_(b)SiO_((3-b)/2)]_(0.2),(C₃H₇SiO_(3/2))_(0.4)[C₃H₇(HO)_(a)SiO_((3-a)/2)]_(0.4)[C₃H₇(C₂H₅O)_(b)SiO_((3-b)/2)]_(0.2),(C₃H₇SiO_(3/2))_(0.4)(CH₃SiO_(3/2))_(0.2)[C₃H₇(HO)_(a)SiO_((3-a)/2)]_(0.32)[C₃H₇(C₂H₅O)_(b)SiO_((3-b)/2)]_(0.08),(C₃H₇SiO_(3/2))_(0.4)((CH₃)₂SiO_(2/2))_(0.2)[C₃H₇(HO)_(a)SiO_((3-a)/2)]_(0.32)[C₃H₇(C₂H₉O)_(b)SiO_((3-b)/2)]_(0.08),and(C₃H₇SiO_(3/2))_(0.4)(C₆H₅SiO_(3/2))_(0.2)[C₃H₇(HO)_(a)SiO_((3-a)/2)]_(0.32)[C₃H₇(C₂H₇O)_(b)SiO_((3-b)/2)]_(0.08)

Component (B) is obtained by hydrolyzing an organoalkoxysilane ororganoalkoxysilanes. For example, it can be produced by hydrolyzingpropyltriethoxysilane, propyltriethoxysilane,propyltri(n-propoxy)silane, propyltri(i-propoxy)silane, or byco-hydrolyzing the aforementioned propylalkoxysilanes with variousalkoxysilanes. Examples of these alkoxysilanes includemethyltrimethoxysilane, methlyltriethoxysilane,methyltri(i-propoxy)silane, dimethyldimethoxysilane, andphenyltrimethoxysilane. The propyltrichlorosilane can also be hydrolyzedin the presence of alcohol. In this case, co-hydrolyzation can becarried out by adding methyltrichlorosilane, dimethyldichlorosilane,phenyltrichlorosilane, or similar chlorosilanes andmethyltriethoxysilane, methyltriethoxysilane,methyltri(i-propoxy)silane, or similar methylalkoxysilane. Alcoholssuitable for these purposes include methanol, ethanol, n-propyl alcohol,i-propyl alcohol, butanol, methoxy ethanol, ethoxy ethanol, or similaralcohols. Examples of hydrocarbon-type solvents which can also beconcurrently used include toluene, xylene, or similar aromatichydrocarbons; hexane, heptane, isooctane, or similar linear or partiallybranched saturated hydrocarbons; and cyclohexane, or similar aliphatichydrocarbons.

Component (B) should be used in an amount of 0.5 to 100 parts by weight,preferably 10 to 70 parts by weight for each 100 parts by weight ofcomponent (A). If it is used in an amount smaller than the lowerallowable limit, it will not be able to reveal its properties. If,however, it is used in an amount exceeding the upper recommended level,too much of component (B) will adhere to the treated product.

The composition of the invention is produced by merely mixing theaforementioned components (A) and (B). If necessary, in addition to theaforementioned components, the composition of the invention may becompounded with various additives. Such additives may include metalsalts of higher fatty acids that antistick characteristics to the fiberyarn, for example magnesium stearate, zinc stearate, calcium stearate,and barium stearate. If necessary, the composition can be combined withanti-corrosive agents and charge-resistant agents. However, thecomposition should not contain ether-modified polyorganosiloxanes, suchas polyorganosiloxane modified with ethylene oxide or polyorganosiloxanemodified with propylene oxide.

Fiber yarn may be treated with the compositions, for example, byimmersion in a treatment bath of the compositions of the inventionfollowed by roll expression, or by bringing the running fiber yarn intocontact with pick-up rolls. The generally preferred add-on amount forthe composition of this invention may be different depending on the typeof the fiber yarn but it is preferably within the range of 0.05 to 9.0wt. %. Types of fiber yarn that can be treated with compositions of theinvention include for example, natural fibers such as wool, silk, flax,cotton, angora, and mohair; regenerated fibers such as Rayon andBemberg; semi-synthetic fibers such as acetate; and synthetic fiberssuch as polyester, polyamide, polyacrylonitrile, polyvinyl chloride,vinylon, polyethylene, polypropylene, and polyurethane (Spandex). Asused herein, the word “yarn” refers to continuous filament thread, spunyarn, or tow.

The straight-oil treatment composition described above is characterizedby improved antistatic properties, excellent compatibility with othercomponents, and improved storage stability. This is achieved due to theuse of the component (B) having a specific molecular structure.Furthermore, since component (B) can be synthesized at a relatively lowcost, the composition of the invention can be advantageously used incommercial production.

The invention will now be described with reference to practicalexamples. In the examples hereinbelow, “parts” denotes “weight parts”,“%” denotes “weight %”, and the viscosity is the value at 25° C. Thestorage stability and compatibility were measured by the methodsdescribed below.

Compatibility—Immediately after preparation, 20 cc of the straight-oilfiber treatment composition was placed in a glass bottle, and itsappearance was visually inspected. The compatibility was rated accordingto the following scale:

◯: denotes homogeneous dissolution and transparency

Δ: denotes slight white turbidity

X: denotes significant white turbidity

Storage Stability—The straight-oil fiber treatment composition wasplaced in a glass bottle and stored for 1 week at 25° C. and then wasinspected visually. The storage stability was rated according to thefollowing scale:

◯: denotes homogeneous dissolution and transparency

Δ: denotes slight separation and precipitation

X: denotes significant separation and precipitation

SYNTHESIS EXAMPLE 1

A four-neck flask equipped with a cooling pipe, thermometer, and astirrer was loaded with 722 g of n-propyltrichlorosilane and 488 g oftoluene. While the components were stirred, a mixture of 137 g of waterand 317 g of isopropyl alcohol was added dropwise. Upon completion ofthe addition, the mixture was heated to 70° C. and stirred for 30 min.The mixture was then cooled, and the separated water layer was removed.The organic layer was then washed three times with water. The productwas combined with 1000 g of water in which 10 g of sodium hydroxide wasdissolved, and the components were mixed for 1 hour and washed threetimes with water. The cooling tube was replaced with a water separationtube, the product was heated, water was azeotropically removed, thesolvent was removed by stripping, and, as result, a highly viscousorganopolysiloxane was obtained. Analysis using ¹³C-NMR, ²⁹Si-NMR, andGPC showed that the obtained organopolysiloxane resin (TP-1) with aweight-average molecular weight of 4800 was represented by the followingconstitutional formula:(n-C₃H₇SiO_(3/2))_(0.58) [n-C₃H₇(HO)_(a)SiO_((3-a)/2)]_(0.31)[n-C₃H₇(i-C₂H₅O)_(b)SiO_((3-b)/2)]_(0.11),where a=1 or 2, and b=1 or 2.

SYNTHESIS EXAMPLE 2

A four-neck flask equipped with a cooling pipe, thermometer, and astirrer was loaded with 722 g of n-propyltrichlorosilane and 488 g oftoluene. While the components were stirred, a mixture of 137 g of water,18 g of methyl-triisopropoxysilane, and 300 g of isopropyl alcohol wasadded dropwise. Upon completion of the addition, the mixture was heatedto 70° C. and stirred for 30 min. The mixture was then cooled, and theseparated water layer was removed. The organic layer was &en washedthree times with water. The product was combined with 1000 g of water inwhich 10 g of sodium hydroxide was dissolved, and the components weremixed for 1 hour and washed three times with water. The cooling tube wasreplaced with a water separation tube, the product was heated, water wasazeotropically removed, the solvent was removed by stripping, and, asresult, a highly viscous organopolysiloxane was obtained. Analysis wing¹³C-NMR, ²⁹Si-NMR, and GPC showed that the obtained organopolysiloxaneresin (TP-2) with a weight-average molecular weight of 4000 wasrepresented by the following constitutional formula:(n-C₃H₇SiO_(3/2))_(0.54)(CH₃SiO_(3/2))_(0.1)[n-C₃H₇(HO)_(a)SiO_((3-a)/2)]_(0.27)[n-C₃H₇(i-C₃H₇O)_(b)SiO_((3-b)/2)]_(0.09),where a=1 or 2, and b=1 or 2.

SYNTHESIS EXAMPLE 3

A four-neck flask equipped with a cooling pipe, thermometer, and astirrer was loaded with 722 g of n-propyltrichlorosilane and 488 g oftoluene. While the components were stirred, 137 g of water was addeddropwise. Upon completion of the addition, the mixture was heated to 70°C. and sired for 30 min. The mixture was then cooled, and the separatedwater layer was removed. The organic layer was then washed three timeswith water. The product was combined with 1000 g of water in which 10 gof sodium hydroxide was dissolved, and the components were mixed for 1hour and washed three times with water. The cooling tube was replacedwith a water separation tube, the product was heated, water wasazeotropically removed, the solvent was removed by stripping, and, asresult, a highly viscous organopolysiloxane was obtained. Analysis using¹³C-NMR, ²⁹Si-NMR and GPC showed that the obtained organopolysiloxaneresin (TP-3) with a weight-average molecular weight of 5000 wasrepresented by the following constitutional formula:(n-C₃H₇SiO_(3/2))_(0.64) [n-C₃H₇(HO)_(a)SiO_((3-a)/2)]_(0.36),

where a 1 or 2.

PRACTICAL EXAMPLE 1

A straight-oil fiber treatment composition was prepared by uniformlymixing 30 g of the organopolysiloxane resin (TP-1) obtained in SynthesisExample 1 and 70 g of liquid paraffin having a viscosity of 12 mm²/s.The obtained straight-oil fiber treatment composition comprised atransparent solution having a viscosity of 24 mm²/s, a specific gravityof 0.87, and a refractory index of 1.453. Compatibility and storagestability of the obtained straight-oil fiber treatment composition weremeasured. Volume resistivity was measured with the use of avolume-resistivity measurement instrument of Hewlett Packard Co. by amethod for measuring volume resistivity (250V/1 min) specified by JISC2101. All results of measurements and evaluation are shown in Table 1.

PRACTICAL EXAMPLE 2

A straight-oil fiber treatment composition was prepared by uniformlymixing 30 g of the organopolysiloxane resin (TP-1) obtained in SynthesisExample 1 and 70 g of liquid paraffin having a viscosity of 17 mm²/s.The obtained straight-oil fiber treatment composition comprised atransparent solution having a viscosity of 30 mm²/s, a specific gravityof 0.91, and a refractory index of 1.456. Compatibility and storagestability of the obtained straight-oil fiber treatment composition weremeasured. Volume resistivity was measured by the same method as inPractical Example 1. All results of measurements and evaluation areshown in Table 1.

PRACTICAL EXAMPLE 3

A straight-oil fiber treatment composition was prepared by uniformlymixing 10 g of the organopolysiloxane resin (PIT-1) obtained inSynthesis Example 1 and 90 g of liquid paraffin having a viscosity of 12mm²/s. Compatibility and storage stability of the obtained straight-oilfiber treatment composition were measured. Volume resistivity wasmeasured by the same method as in Practical Example 1. All results ofmeasurements and evaluation are shown in Table 1.

PRACTICAL EXAMPLE 4

A straight-oil fiber treatment composition was prepared by uniformlymixing 20 g of the organopolysiloxane resin (TP-1) obtained in SynthesisExample 1 and 80 g of liquid paraffin having a viscosity of 12 mm²/s.Compatibility and storage stability of the obtained straight-oil fibertreatment composition were measured. Volume resistivity was measured bythe same method as in Practical Example 1. All results of measurementsand evaluation are shown in Table 1.

PRACTICAL EXAMPLE 5

A straight-oil fiber treatment composition was prepared by uniformlymixing 30 g of the organopolysiloxane resin (TP-2) obtained in SynthesisExample 2 and 70 g of liquid paraffin having a viscosity of 12 mm²/s.The obtained straight-oil fiber treatment composition was transparent.Compatibility and storage stability of the obtained straight-oil fibertreatment composition were measured. Volume resistivity was measured bythe same method as in Practical Example 1. All results of measurementsand evaluation are shown in Table 1.

PRACTICAL EXAMPLE 6

A straight-oil fiber treatment composition was prepared by uniformlymixing 30 g of the organopolysiloxane resin (TP-1) obtained in SynthesisExample 1 and 70 g of an oil of polydimethylsiloxane having bothmolecular terminals capped with trimethylsiloxy groups and having aviscosity of 10 mm²/s. Compatibility and storage stability of theobtained straight-oil fiber treatment composition were measured. Volumeresistivity was measured by the same method as in Practical Example 1.All results of measurements and evaluation are shown in Table 1.

COMPARATIVE EXAMPLE 1

A straight-oil fiber treatment composition was prepared by uniformlymixing 30 g of the organopolysiloxane resin (IP-3) obtained in SynthesisExample 3 and 70 g of liquid paraffin having a viscosity of 12 mm²/s.The obtained straight-oil fiber treatment composition comprises asemitransparent solution with a noticeable precipitation. Compatibilityand storage stability of the obtained straight-oil fiber treatmentcomposition were measured. All results of measurements and evaluationare shown in Table 1.

COMPARATIVE EXAMPLE 2

Storage stability was measured for a strait-oil fiber treatmentcomposition that comprised 100 g only of liquid paraffin of a viscosityof 12 mm²/s. Volume resistivity was measured by the same method as inPractical Example 1. All results of measurements and evaluation areshown in Table 1. TABLE 1 (A) (B) Storage Volume Type Content % TypeContent % Compatibility Stability Resistivity Evaluation Pr. Ex. 1 A-170 TP-1 30 ◯ ◯ 2 × 10¹³ Good Pr. Ex. 2 A-2 70 TP-1 30 ◯ ◯ 2 × 10¹³ GoodPr. Ex. 3 A-1 90 TP-1 10 ◯ ◯ 4 × 10¹³ Good Pr. Ex. 4 A-1 80 TP-1 20 ◯ ◯3 × 10¹³ Good Pr. Ex. 5 A-1 70 TP-2 30 ◯ ◯ 3 × 10¹³ Good Pr. Ex. 6 A-370 TP-1 30 ◯ ◯ 3 × 10¹³ Good Comp. Ex. 1 A-1 70 TP-3 30 Δ Δ —Unsatisfactory (insufficient compatibility and storage stability) Comp.Ex. 2 A-1 100 — 0 — ◯ 4 × 10¹⁴ Unsatisfactory (insufficient antistaticproperties)* Types of component (A):A-1: liquid paraffin of 12 mm²/s viscosityA-2: liquid paraffin of 17 mm²/s viscosityA-3: polydimethylsiloxane oil of 10 mm²/s viscosity

The straight-oil treatment composition of the invention, which hasaforementioned main components (A) and (B), is characterized byexcellent component compatibility, storage stability, and anti-staticproperties.

1. A straight-oil finishing composition comprising (A) 100 parts byweight of a polydimethylsiioxane oil or liquid paraffin having aviscosity of 3 to 70 mm²/s at 25° C.; and (B) 0.5 to 100 parts by weightof an organopolysiloxane resin, which contains silanol groups andsilicon-bonded alkoxy groups and wherein 20 mole % or more of allsiloxane units are siloxane units represented by formula C₃H₇SiO_(3/2).2. The straight-oil finishing composition of claim 1, where in component(B) the amount of silanol groups is greater than the amount of thesilicon-bonded alkoxy groups.
 3. The straight-oil finishing compositionaccording to claim 1, where said alkoxy groups of component (B) arealkoxy groups having 3 to 8 carbon atoms.
 4. The straight-oil finishingcomposition according to claim 1, where said component (A) is liquidparaffin.
 5. The straight-oil finishing composition of claim 1, wheresaid component (B) contains both siloxane units represented by formulaC₃H₇SiO_(3/2) and C₃H₇(HO)_(a)(R′O)_(b)SiO_((3-a-b)/2), wherein 20-95mole % of all siloxane units are siloxane units represented by formulaC₃H₇SiO_(3/2) and 5-80 mole % of all siloxane units are siloxane unitsrepresented by formulaC₃H₇(HO)_(a)(R′O)_(b)SiO_((3-a-b)/2), where each R′ is independentlyselected from alkyl groups having 1 to 8 carbon atoms andalkyloxyalkylene groups having 1 to 8 carbon atoms, 0<a≦2, 0<b≦2,0<(a+b)≦2.
 6. The straight-oil finishing composition of claim 1, wheresaid component (B) is represented by the following averageconstitutional formula:(C₃H₇SiO_(3/2))_(x)[C₃H₇(HO)_(a)(R′O)_(b) SiO_((3-a-b)/2)]_(y){R_(c)SiO_((4-c/2))}_(z), where each R′ is independently selected fromalkyl groups having 1 to 8 carbon atoms and alkyloxyalkylene groupshaving 1 to 8 carbon atoms, and each R is independently selected fromphenyl groups, alkyl groups having 1 to 10 carbon atoms, hydroxylgroups, and alkoxy groups, 0<a≦2, 0<b≦2, 0<(a+b)≦2, c is between 0 and3, x>0, y>0, z≧0, (x+y+z)=1, and x/(x+y+z)≧0.2.
 7. A fiber yarn treatedwith the straight-oil finishing claim 1.